She was betrothed to Claudius sometime after his first engagement to his relative Aemilia Lepida was broken by Augustus in 8 AD, due to the disgrace of Aemilia's parents. Tiberius probably pushed for the new betrothal in order to reward his friend with a connection to the imperial family. The betrothal of Medullina and Claudius is confirmed outside the written records by an extant inscription erected by Medullina's pedagogue. The dedication is to "Medullina Camilli f. Ti Claudi Neronis Germanici sponsa (Medullina, daughter of Camillus, betrothed of Ti. Claudius Nero Germanicus)."

Suetonius states that Medullina unexpectedly fell ill and died on the day of her wedding to Claudius, possibly in 9 or 10 AD.

By a strange coincidence, Medullina's brother Scribonianus was the instigator of the first major coup d'etat attempt of Claudius' reign, while governor of Dalmatia in 42 AD.

Livia Medullina is referred to in Robert Graves' novel I, Claudius as Medullina Camilla, she is depicted as an early love of Claudius who is able to look past his infirmities. Against Livia's wishes Claudius is permitted to marry Camilla by Germanicus and Augustus, but is robbed of happiness on the day of their engagement as she is assassinated for an unrelated vendetta against Camilla's father.